Bleaching composition



United States Patent 3,346,502 BLEACHING COMPOSITION Harold EugeneWixou, New Brunswick, N.J., assignor to Colgate-Palmolive Company, NewYork, N.Y., a corporation of Delaware No Drawing. Filed Apr. 27, 1965,Ser. No. 451,348 5 Claims. (Cl. 252-102) This application is acontinuation-in-part of application Ser. No. 172,121, filed Feb. 9,1962, now abandoned.

The present invention relates to bleaching compositions. Moreparticularly, it relates to bleaching compositions in the form of drywater soluble compositions, preferably in the form of powders, and towater soluble packets containing such powders.

In accordance with the present invention, a bleaching compositioncomprises a dry water soluble compound which, on contact with water,liberates hypochlorite chlorine, ultramarine blue, and a substantivefluorescent brightener stable in the presence of saidhypochloritechlorine agent. Typically, the instant dry compositionscomprise from 1 to about 99 percent by Weight of thehypochlorite-liberating compound, about 0.05 to 5 percent by weight ofultramarine blue, and about 0.01 to 5 percent of fluorescent brightener.Preferably the composition is packaged within a sealed envelope of watersoluble polyvinyl alcohol film.

Also within the scope of the present invention is a process forimproving the appearance of textiles which comprises bleaching a textilewith an aqueous hypochlorite solution While simultaneously applying tosaid textile from said solution ultramarine blue and a fluorescentbrightener stable in the presence of hypochlorite and substantive tosaid textile.

The instant dry compositions are highly advantageous in that theultramarine blue pigment therein, which is employed in an amountsuflicient visibly to whiten fabrics viewed under artificialillumination substantially devoid of ultraviolet radiation, deposits onfabrics bleached therewith and overcomes any yellowing which is notremoved during the bleaching treatment or which may have been impartedto the fabric by repeated treatments or by the substantive fluorescentdye. Use of the present bleaching compositions in household launderingcompensates for the destructive action of hypochlorite bleaches on manyfluorescent dyes used in conventional detergent compositions, andsupplements the brightening action of a detergent composition which maycontain a bleachstable fluorescent brightener. In addition, textilesbleached with the instant compositions exhibit particularly improvedappearance and whiteness when viewed by illumination having a lowcontent of ultraviolet energy, thus effecting an improved, balancedwhitening to fabrics irrespective of whether they are viewed undernatural daylight, artificial illumination of low ultraviolet content orvarious mixtures thereof.

The preferred water soluble packet form of the instant product olfersthe advantage of providing a highly effective chlorine-type bleachingagent in a dry form. These packets avoid the dustiness of powderedproducts, and the likelihood or dangers of spillage or splatteringcharacteristic of liquid products. In use, the entire packet is droppedinto a washing machine containing water and clothes to be bleachedwithout any need for premeasuring by the housewife.

These packets also avoid the necessity for handling of bulky or heavycontainers of glass or fiberboard cartons by the housewife and providean effective means of masking the characteristic and sometimesirritating odor of chlorine-liberating bleaches. Moreover, use of thesepackets eliminates the possibility of contact of thehypochlorite-liberating bleach with the skin of the user, which isespecially desirable in cases of those people who are allergic tohypochlorites.

The preferred packets offer the further outstanding advantage that theproduct container, i.e. the polyvinyl alcohol film in envelope form,contributes considerable soil antiredeposition properties to the systemand thus the packets are specially suited for use in conjunction withsoap and detergent products in connection with the washing and bleachingof soiled clothes. The use of water soluble polyvinyl alcohol film isalso advantageous in that it is thermoplastic and may readily be heatsealed, it offers high resistance to permeability by gases, it hasexcellent oil and grease resistance, long shelf life, and it can easilybe printed with alcohol-type inks.

Hypochlorite-generating agents suitable for use in the compositions ofthe present invention are those water soluble dry solid materials whichgenerate hypochlorite ion on contact with, or dissolution in Water.Examples thereof are the dry, particulate heterocyclic N-chlor imidessuch as trichlorocyanuric acid, dichlorocyanuric acid and salts thereofsuch as sodium dichlorocyanurate and potassium dichlorocyanurate. Otherimides may also be used such as N-chlorosuccinimide, N-chloromalonimide, N-chloro phthalimide and N-chloro naphthalimide. Additionalsuitable imides are the hydantoins such as 1,3 dilchloro 5,5 dimethylhydantoin; N-monochloro- C,C dimethylhydantoin; methylene-bis(Nchloro-C,C- dimethylhydantoin); 1,3 dichloroS-methyl-S-isobutylhydantoin; 1,3-dichloro-5 methyl-S-ethylhydantoin;1,3- dichloro-S-methyl-Sn-amylhydantoin, and the like. Other usefulhypochlorite-liberating agents are trichloromelamine and dry,particulate, water soluble anhydrous inorganic salts such as lithiumhypochlorite and calcium hypochlorite. These hypochlorite-generatingagents are employed in the form of small particles substantially all ofwhich are less than about 1 millimeter in diameter, and desirably lessthan about 0.5 millimeter in diameter, thus ensuring rapid solubility ofthe particles and mini mizing excessive localized hypochloriteconcentrations and resulting pinholing on use of these compositions. Theinstant chlorine liberating agents are employed in a proportion, withinthe range, indicated above, such as to yield a product which containsfrom about 1 to about 20% available chlorine on a total weight basis,although other proportions may be employed if desired.

The instant ultramarine blue pigment is stable in the presence of thehypochlorite-liberating agent during both storage and use of the instantcompositions. The pigment is in the form of particles substantially allof which ex hibit a diameter of less than about 0.05 millimeter, and ischaracterized by the ability to impart a faint blue visible shade tofabrics treated therewith Without staining such fabrics when used atrecommended concentration and fashion, being generally considered to benon-substantive, or at least non-accumulative, on fabrics. The instantultramarine blue pigment is readily dispersible in water underconditions of use, and does not cause visible spotting of fabricstreated therewith.

The Ultramarine blue particles are employed in a proportion such that onuse of the final product as directed in a home washing machine undernormal conditions, a typical load of Wash is exposed to .05 to 0.5 gramthereof. Inasmuch as household washing machines generally are filledfrom 10 to 20 gallons of water during washing or a deep rinse, desirableproportions of bluing in the instant compositions has been found to bebetween .05 and 5 percent by weight thereof.

The fluorescent brighteners or optical dyes used in the instantcompositions are substantive to textiles, e.g. cotton, and are resistantto attack by the hypochloriteliberating agent. Such brighteners are ofparticular assistance in connection with the bleaching of textiles orfabrics viewed under illumination wherein the visible bluing actionsupplied by the ultramarine is subject to being supplemented by ablue-fluorescent optical bleach. Examples of suitable suchtextile-substantive optical bleaches, which may be present in amounts onthe order of about 0.01 to 5 percent by Weight of the composition, aretriazole compounds such as sulfonated 3,7-diaminodibenzothiophenedioxide such as I-ISOa SOaH and bisbenzimidazoles such as JHzCEhOH HAlthough for convenience the acid forms of certain of these compoundsare depicted, it will be appreciated that these formulas as used hereinare also indicative of suitable salts thereof compatible with theremaining constituents of the instant products, such as, e.g., thesodium salts.

In the instant compositions, the hypochlorite-liberating agents,fluorescent dye, and ultramarine blue particles co-act to produce on useof the product, bleached cotton fabrics having surprising andunexpectedly high visible whiteness characteristic under widely varyingconditions of illumination.

The instant compositions suitably may contain additional constituentssuch as water soluble organic surface active agents which are stable inthe presence of the hypochlorite generating agent. Such detergents maybe anionic detergent salts having alkyl substituents of 8 to 22 carbonatoms such as the water soluble higher fatty acid alkali metal soaps, egsodium myristate and sodium palmitate; water soluble sulfated andsulfonated anionic alkali metal and alkaline earth metal detergent saltscontaining a hydrophobic higher alkyl moiety (typically containing fromabout 8 to 22 carbon atoms) such as salts of higher alkyl monoorpoly-nuclear aryl sulfonates having from about 10 to 16 carbon atoms inthe alkyl group (e.g. sodium dodecylbenzene sulfonate, magnesiumtridecylbenzene sulfonate, lithium or potassium pentapropylene benezenesulfonate); alkali metal salts of higher alkyl napthalene sulfonicacids; sulfated higher fatty acid monoglycerides such as the sodium saltof the sulfated monoglycerides of coconut oil fatty acids and thepotassium salt of the sulfated monoglyceride of tallow fatty acids;alkali metal salts of sulfated fatty alcohols containing from about 10to 18 carbon atoms (e.g. sodium lauryl sulfate and sodium stearylsulfate); alkali metal salts of higher fatty acid esters of lowmolecular weight alkylol sulfonic acids, e.g. fatty acid esters of thesodium salt of isethionic acid; the fatty ethanolamide sulfates; thefatty acid amides of amino alkyl sulfonic acids, e.g. lauric acid amideof taurine; as well as numerous other ionic organic surface activeagents such as sodium toluenesulfonate, sodium xylenesulfonate, sodiumnaphthalene sulfonate; and mixtures thereof. In general these organicsurface active agents are employed in the form of their alkali metalsalts or alkaline earth metal salts as these salts possess the requisitestability, solubility, and low cost essential to practical utility.

Amphoteric or cationic detergents may also be employed in the instantproducts, examples thereof being sodium N-lauryl beta alanine and cetylpyridinium chloride respectively.

The proportion of organic surface active agent which is used may varywidely, typically being from about 2 to 20% by weight of thecomposition.

The presence of inorganic salts in the instant bleach compositions isdesirable in that the inorganic salt may serve to adjust pH and also toact as a carrier or dispersion medium for the bleaching agent and forany stabilizing olefin therefor which may be employed. Water solubleinorganic salts suitable for use in the instant compositions includesodium sulphate, sodium chloride, a1- kaline detergent builder saltshaving a pH of from 8 to 11 or above such sodium carbonate, borax, andsodium silicate, alkali metal orthophosphates, and polyphosphates suchas monosodium phosphate, trisodium phosphate, tetrasodium pyrophosphate,pentasodium tripolyphosphate, and acid salts such as sodium bisulphate.The presence of sodium carbonate or sodium metasilicate in the instantpackets has been found to aid in the retention of the Water solublecharacteristics of these packets, sodium carbonate being especiallybenefiicial in that on dissolution in water, it reacts with any acidiccomponents present (e.g. in the hypochloride generating agent) toproduce bubbles of carbon dioxide gas which contribute a desirablemixing and agitating action.

The instant compositions should be dry, i.e. desirably they contain lessthan 1 percent and preferably less than 0.5 percent moisture, in orderto minimize decomposition of the hypochlorite-liberating agent prior touse of the composition, and desirably also should be soluble ordispersible in water under conditions of usage relatively quickly, e.g.Within about 30 seconds in the case of a normal charge thereof (ca. 40grams) to a household washing machine. One Way of achieving such rapiddispersion and solution rate is to incorporate one of the aforesaidsurface active agents and to prepare the composition in particulate formof small particle size, such finely divided particulate product having amaximum particle diameter of about 0.5 millimeter.

The instant compositions may contain further optional ingredients suchas, inter alia, organic sequestrants such as ethylene diaminetetraacetic acid and its salts, sodium carboxymethyl cellulose, citricacid, resins and polymers such as polyvinyl pyrrolidone, polyacrylatesand the like, starch, urea, perfumes, corrosion inhibitors, coloringmatter, and the like.

Example I The following product is highly effective in improving theappearance of both whiteand bleach-fast colored cottons:

Parts by Weight Pentasodium tripolyphosphate 30.00 Alkylaryl sulfonate(containing 76 percent sodium tridecyl benzene sulfonate, 9.9 percentsodium silicate, 10.8 percent sodium sulfate, and 3.3 percent moisture)2.62 Fluorescent dye 0.16

The composition is a mechanically dry-mixed finely divided powder havinga maximum particle size of less than 0.5 millimeter. The ultramarineblue pigment has an extremely small particle size, at least 99.5 percentby weight thereof having a particle diameter of less than 0.05millimeter.

Forty grams of this formulation are heat sealed within an envelope ofcommercial polyvinyl alcohol film which has been prepared by ahydrolysis of polyvinyl acetate. This polyvinyl alcohol contains about15 percent of unhydrolyzed vinyl acetate, and is devoid of ethoxylation.

In use, the entire packet is dropped into a household washing machine(containing white household linens including bed sheets, pillow cases,and towels) at the start of a ten-minute washing period. The water usedhas a hardness of 150 ppm. and a temperature of about 120 F. Acommercial heavy duty detergent composition is present in aconcentration of 0.15 percent, and the concentration of the instantcomposition is 0.05%. The packet promptly dissolves, forming ahypochlorite solution containing the bleach-stable fluorescent dye andthe ultramarine blue, which cooperate to produce cotton textiles ofsubstantially improved appearance, i.e., a highly whitened or brightenedappearance to the eye.

Example 11 The powder composition of Example I may be replaced by thefollowing, which exhibits the same particle size characteristics:

Percent Pentasodium tripolyphosphate 30.00 Sodium carbonate 5.00 Sodiumsulfate, anhydrous 40.6 15 Fluorescent brightener of Example I 0.16Ultramarine blue pigment 0.375 Alkylarylsulfonate of Example I 2.62Perfume 0.25 Limonene 0.25 Potassium dichlorocyanurate 20.60 Mineral oil0.13

Example III Packets may be prepared and used as in Example I utilizingthe following dry powder composition:

omo-O-oonn s/ 6 The composition is a mechanically dry-mixed finelydivided powder having a maximum particle size of less than 0.5millimeter. The ultramarine blue pigment has an extremely small particlesize, at least 99.5 percent by Weight thereof having a particle diameterof less than 0.05 millimeter.

Example IV The powder composition of Example III may be modified bydirect substitution of particulate trichlorocyanuric acid having aparticle diameter of less than 0.5 millimeter for the potassiumdichlorocyanurate of that example.

Example V The following composition is prepared in the form of aneifervescing tablet by admixing 65 parts thereof with 35 parts ofconventional effervescing agents such as citric acid and soda ash andcompressing the dry mixture in tablet form.

A nine-pound load of soiled household linens are simultaneously washed,bleached, and blued in a conventional household automatic washingmachine in which the wash water contains approximately 0.15% by weightof the following:

Parts by weight Nonyl phenol ethylene oxide condensation productcontaining an average of 9.5 moles of ethylene oxide per mole ofcondensation product 4.47 Pentasodium tripolyphosphate 37.38 Sodiummetasilicate, anhydrous 37.38 Sodium carboxy methyl cellulose 2.39Chlorine-bleach stable fluorescent 'brightener of Example I 0.30Potassium dichlorocyanurate 14.92 Limonene 0.24 Ultramarine blue pigment0.24

Examples VII-X I V The following table sets forth dry compositions whichexemplify additional specific embodiments of the instant invention,being prepared in the form of uniform mixtures of the componentsindicated in a particulate form having a particle diameter of less thanabout 0.5 millimeter. The ultramarine blue pigment employed ischaracterized by a particle diameter of less than 0.05 mil-limeter suchthat the pigment does not cause visible spotting of fabrics treatedtherewith. All proportions and parts are by weight.

TABLE.-EXAMPLES VIIXIV VII VIII IX X XI XII XIII XIV Potassiumdlchloroeyanurate 20. 20.00 97 7 'Irichlorocyanuric acid 5.00 1,3diohloro 5,5 dimethyl hy 'm 10.00 Lithium hypochlorite. 50. 00Chlorinated trisodium ph nsnbate N,N dichloro p-toluene sulfonamido.Hypochlorite-stable fluorescent brighteuer:

Triazole type 0. 0. 10 0 Bisbenzimidazole type Ultramarine bluepigment..- 0.30 0. 10 0.15 0.20 0.10 0.90 0. 1. 6 Sodium sulfate 79. 5094. 83 89. 75 49. 68 4. 85 23. 50 79. 95

N S03 Na CHzCHzOH H While there has been disclosed that which at presentis considered to be the preferred embodiment of the invention, it willbe understood, of course, that changes, modifications, or substitutionsmay be made therein without departing from the true scope of theinvention as defined in the appended claims.

What is claimed is:

1. A bleaching composition consisting essentially of from about 1 to 99percent by weight of a heterocyclic N-chloroimide selected from thegroup consisting of trichlorocyanuric acid, dichlorocyanuric acid andsalts thereof, about 0.01 to 5 percent by Weight of a fluorescentbrightener substantive to cotton and stable in the presence of saidN-chloroimide selected from the group consisting of l CHaOHaOH H andultramarine blue pigment of a particle diameter less than 0.05millimeter in an amount from about 0.05 to 5 percent by weightsufficient to impart a faint blue shade to fabrics treated with anaqueous solution of said composition, said composition being in the formof a finely divided particulate product having a maximum particlediameter of about 0.5 millimeter so as to be readily dispersible inwater when used in a household Washing machine.

2. A bleaching composition consisting essentially of about 1 to 99percent by weight of potassium dichlorocyanurate, about 0.01 to 5percent of a fluorescent brightener having the structure and ultramarineblue pigment of a particle diameter less than 0.05 millimeter in anamount from about 0.5 to 5 percent by weight sufficient to impart afaint blue shade to fabrics treated with an aqueous solution of saidc0mposition, said composition being in the form of a finely dividedparticulate product having a maximum particle diameter of about 0.5millimeter so as to be readily dispersible in water when used in ahousehold washing machine.

3. A bleaching composition consisting essentially of from about 1 to 99percent by weight of a dry watersoluble compound which, on contact withwater, liberates hypochlorite-chlorine, about 0.01 to 5 percent byweight of a fluorescent brightener substantive to cotton and stable inthe presence of said hypochlorite-chlorine liberating agent selectedfrom nsoa- SO3H onao-Ocorrn- \S/ NHCO-O-OCI-I O:

and

l l CHaCHzOH H and ultramarine blue pigment of a particle diameter lessthan 0.05 millimeter in an amount from about 0.05 to 5 percent by weightsufiicient to impart a faint blue shade to fabrics treated with anaqueous solution of said composition, and about 2 to 30 percent of aWater-soluble organic anionic surface-active agent stable in thepresence of the hypochlorite-chlorine liberating agent, said compositionbeing in the form of a finely divided particulate product having amaximum particle diameter of about 0.5 mil-limeter so as to be readilydispersible in water when used in a household washing machine.

4. A bleaching composition consisting essentially of from 1 to 99percent by weight of a dry water-soluble compound which, on contact withwater, liberates hypochlorite-chlorine, about 0.01 to 5 percent byWeight of a fluorescent brightener substantive to cotton and stable inthe presence of said hypochlorite-chlorine liberating agent selectedfrom the group consisting of N SOaH Hso3 SOaH cnaoO-oomp NHO o-Ooom sand ultramarine blue pigment of a particle diameter less than 0.05millimeter in an amount from about 0.05 to 5 percent by weightsuflicient to impart a faint blue shade to fabrics treated with anaqueous solution of said composition, and about 2 to 30 percent ofsodium tridecyl benzene sulfonate, said composition being in the form ofa finely divided particulate product having a maximum particle diameterof about 0.5 millimeter so as to be readily dispersible in water whenused in a household washing machine.

5. A bleaching composition consisting essentially of about 1 to 99percent by weight of a dry water-soluble compound which, on contact withwater, liberates hypochlorite-chlorine, about 0.01 to 5 percent byweight of a fluorescent brightener substantive to cotton and stable inthe presence of said hypochlorite liberating agent, and ultramarine bluepigment of a particle diameter less than 0.05 millimeter in an amountfrom about 0.05 to 5 percent by weight suflicient to impart a faint blueshade to fabrics treated with an aqueous solution of said composition,said composition being in the form of a finely divided particulateproduct having a maximum particle diameter of about 0.5 millimeter so asto be readily dispersible in water when used in a household washingmachine.

References Cited UNITED STATES PATENTS 2,635,400 4/1953 Abbott et a125293 XR 2,636,008 4/1953 Jurgenson et al. 25293 XR 2,702,759 3/1957Scalera et al. 252-3013 XR 2,784,183 3/1957 Keller et ,al. 252301.3 XR2,930,760 3/1960 Gebhardt 252-117 XR 3,112,274 11/1963 Morganthaler eta1. 25299 FOREIGN PATENTS 3/1955 Canada.

JULIUS GREENWALD, M. WEINTBLATT,

Examiners.

1. A BLEACHING COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 1 TO 99PERCETN BY WEIGHT OF A HETEROCYCLIC N-CHLOROIMIDE SELECTED FROM THEGROUP CONSISTING OF TRICHOROCYANURIC ACID, DICHLOROCYANURIC ACID ANDSALTS THEREOF, ABOUT 0.01 TO 5 PERCENT BY WEIGHT OF A FLUORESCENTBRIGHTENER SUBSTANTIVE TO COTTON AND STABLE IN THE PRESENCE OF SAIDN-CHLOROIMIDE SELECTED FROM THE GROUP CONSISTING OF